Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Organic acids play a key role in the troposphere, contributing to atmospheric aqueous-phase chemistry, aerosol formation, and precipitation acidity. Atmospheric models currently account for less than half the observed, globally averaged formic acid loading. Here we report that acetaldehyde photo-tautomerizes to vinyl alcohol under atmospherically relevant pressures of nitrogen, in the actinic wavelength range, λ = 300–330 nm, with measured quantum yields of 2–25%. Recent theoretical kinetics studies show hydroxyl-initiated oxidation of vinyl alcohol produces formic acid. Adding these pathways to an atmospheric chemistry box model (Master Chemical Mechanism) demonstrates increased formic acid concentrations by a factor of ~1.7 in the polluted troposphere and a factor of ~3 under pristine conditions. Incorporating this mechanism into the GEOS-Chem 3D global chemical transport model reveals an estimated 7% contribution to worldwide formic acid production, with up to 60% of the total modeled formic acid production over oceans arising from photo-tautomerization

Observation of Air Pollution over China Using the IASI Thermal Infrared Space Sensor

Part of the ISSI Scientific Report Series volume 16International audienceIn this chapter we describe what is achievable in terms of pollutant tracking from space using observations provided by thermal infrared remote sensors. After a general introduction on infrared remote sensing, we exploit the data provided by the Infrared Atmospheric Sounding Interferometer (IASI) missions onboard the Metop series of satellite to illustrate pollution detection at various spatial and temporal scales. Then, we focus on air pollution over China and discuss three case studies involving different pollutants. The first example discusses the geophysical conditions for detection of ammonia (NH3) and sulfur dioxide (SO2), both precursors of particulate matter (PM). The second case illustrates the seasonal variation of ozone (O3), in particular during the monsoon period. The third case shows the local accumulation of enhanced levels of carbon monoxide (CO) when pollution episodes occur

Advances in understanding, models and parameterizations of biosphere-atmosphere ammonia exchange

Atmospheric ammonia (NH3) dominates global emissions of total reactive nitrogen (Nr), while emissions from agricultural production systems contribute about two-thirds of global NH3 emissions; the remaining third emanates from oceans, natural vegetation, humans, wild animals and biomass burning. On land, NH3 emitted from the various sources eventually returns to the biosphere by dry deposition to sink areas, predominantly semi-natural vegetation, and by wet and dry deposition as ammonium (NH4+) to all surfaces. However, the land/atmosphere exchange of gaseous NH3 is in fact bi-directional over unfertilized as well as fertilized ecosystems, with periods and areas of emission and deposition alternating in time (diurnal, seasonal) and space (patchwork landscapes). The exchange is controlled by a range of environmental factors, including meteorology, surface layer turbulence, thermodynamics, air and surface heterogeneous-phase chemistry, canopy geometry, plant development stage, leaf age, organic matter decomposition, soil microbial turnover, and, in agricultural systems, by fertilizer application rate, fertilizer type, soil type, crop type, and agricultural management practices. We review the range of processes controlling NH3 emission and uptake in the different parts of the soil-canopy-atmosphere continuum, with NH3 emission potentials defined at the substrate and leaf levels by different [NH4+] /[H+] ratios (Γ). Surface/atmosphere exchange models for NH3 are necessary to compute the temporal and spatial patterns of emissions and deposition at the soil, plant, field, landscape, regional and global scales, in order to assess the multiple environmental impacts of airborne and deposited NH3 and NH4+ . Models of soil/vegetation/atmosphere NH3 exchange are reviewed from the substrate and leaf scales to the global scale. They range from simple steady-state, “big leaf” canopy resistance models, to dynamic, multi-layer, multi-process, multi-chemical species schemes. Their level of complexity depends on their purpose, the spatial scale at which they are applied, the current level of parameterization, and the availability of the input data they require. State-of-the-art solutions for determining the emission/sink Γ potentials through the soil/canopy system include coupled, interactive chemical transport models (CTM) and soil/ecosystem modelling at the regional scale. However, it remains a matter for debate to what extent realistic options for future regional and global models should be based on process-based mechanistic versus empirical and regression-type models. Further discussion is needed on the extent and timescale by which new approaches can be used, such as integration with ecosystem models and satellite observations